Method and compositions for bleaching hair

ABSTRACT

An emulsion hair bleach composition prepared by combining an aqueous oxidizing agent composition, a persulfate composition, and, optionally, a bleach oil composition, in amounts sufficient to provide a mixture containing an active oxygen concentration of about 3 to 5% by weight of the total mixture, a total alkalinity concentration of about 0.7–1.2 meq/gm., and 0.5–20% by weight of the total mixture of an oil having a solubility parameter of 5–12 (cal/cm 3 ) 1/2 ; an emulsion hair bleach composition capable of lightening hair in 10 to 30 minutes, and a kit for use in bleaching hair.

This is a continuation of application(s) Ser. No. 10/115,497, filed Apr.3, 2002 now U.S. Pat. No. 6,703,004.

TECHNICAL FIELD

The invention is in the field of methods and compositions for bleachinghair.

BACKGROUND OF THE INVENTION

Women have been bleaching their hair for thousands of years. Some of theprimitive concoctions used to bleach hair in early Rome, prior to thebeginning of the Christian era, included native minerals such as alum,soda, and wood ash combined with wine dregs or water. Such preparationswere often left on the hair for several days, and lightened very darkhair to a desirable reddish gold in color. A number of books publishedduring the Renaissance also disclose various formulas for bleachinghair. Typically these compositions were based upon ingredients such asalum, borax, or soda, in combination with plant extracts. It has alsobeen reported that Venetian women obtained their blond hair by spongingit with a solution of soda (or rock alum, black sulfur, and honey)through the hair, spread it over the broad brim of a crownless hat, andlet it dry in the sunlight [Cosmetics: Science and Technology, SecondEdition, Volume 2, 1972]. This treatment persisted for hundreds of yearsthereafter, until the fashions changed.

Modern hair bleaches are much milder and non-toxic when compared totheir historical counterparts. The key ingredient is a mild oxidizingagent, which is most often hydrogen peroxide. Hydrogen peroxide exertsboth a chemical and physical effect on the hair. It is capable ofpenetrating the hair cuticle and oxidizing the melanin (which providescolor) so that the hair becomes noticeably lighter. If treated for along enough period of time, hair can be colored to very light blonde orwhite, although it has been said that hair bleached with hydrogenperoxide only may tend to exhibit a yellowish tinge.

Currently, hair bleaches are most commonly found in the two componentkit form. One component comprises an aqueous based hydrogen peroxidecontaining solution or emulsion. The second component comprises apowdered bleach composition that contains persulfate salts which act asaccelerators of the bleaching process when the two components arecombined. The hydrogen peroxide and persulfates are very reactive whencombined and form nascent oxygen in addition to hydrogen and sodiumsulfide. The nascent oxygen greatly facilitates oxidizing and bleachingof melanin from the hair. Typical bleaches generally have a pH of 9 to11 and are applied to hair for 30 to 60 minutes to achieve the desiredresults.

While modern bleaches are significantly improved when compared to theirpre-historic counterparts, there are still many need gaps in thestandard bleaching process. One chronic consumer complaint is that thebleaching process takes too long. The 30 to 60 minutes required issimply too inconvenient for modern time-pressed consumers. In addition,the high pH and oxidizing agents may cause damage to those who haveoverly sensitive hair, particularly with repeat procedures. Accordingly,the gold standard for hair bleach is to provide bleach compositions thatwork in as short a time period as possible without damaging the hair,and at the same time achieving optimal lightening of hair.

It has been discovered that if the bleach composition applied to thehair has certain specific properties, the amount of time required tobleach the hair can be significantly reduced and the resultingcomposition is much “kinder” to the hair, even providing a conditioningeffect.

Three parameters have been defined as contributing to a shorted timeperiod to achieve hair bleaching. The first parameter is the activeoxygen concentration in the bleach composition. As previously noted, itis nascent, or active, oxygen that causes bleaching of the melanin inthe hair fiber. If the bleach composition does not contain an adequatelevel of active oxygen, the bleach will not adequately lighten hair. Thesecond parameter is total alkalinity concentration. It has been foundthat the proper concentration of alkaline ingredients promotes openingof the hair cuticle and facilitates penetration of active oxygen intothe hair fiber. Compositions that do not exhibit sufficient alkalinityare not as effective in lightening hair because the hair cuticle is notas penetrable. However, the amount of total alkalinity cannot be toohigh otherwise the composition can potentially cause irritation to skinand scalp. The third parameter that has an impact on optimal bleachingof the hair is the presence of a hydrophobic oil in the bleachcomposition. It has been discovered that the hydrophobic oil promotesmore effective penetration of the active components into the hair shaft.Without being bound by this explanation, it is believed that thehydrophilic, water soluble bleach active ingredients are preferentiallyabsorbed into the hair shaft because of their insolubility andincompatibility with the hydrophobic oil which “pushes” the watersoluble ingredients away and into the hair shaft. The hydrophobic oilthen deposits on the hair fibers and exerts a conditioning effect.

It is an object of the invention to provide a bleach composition thatbleaches the hair in a reduced amount of time, prepared by combining anaqueous oxidizing agent composition, a persulfate composition, andoptionally, an oil composition.

It is a further object of the invention to provide a bleach compositionthat contains a hydrophobic oil in an amount sufficient to causepreferential penetration of active ingredients into the hair shaft.

It is a further object of the invention to provide a bleach compositionthat also conditions the hair.

SUMMARY OF THE INVENTION

The invention is directed to an emulsion hair bleach compositionprepared by combining (i) an aqueous oxidizing agent composition, (ii) apersulfate composition, and, optionally, (iii) a bleach oil composition,in amounts sufficient to provide a mixture containing:

(a) an active oxygen concentration of about 3 to 5% by weight of thetotal mixture,

(b) a total alkalinity concentration of about 0.7–1.2 meq/gm., and

(c) 0.5–20% by weight of the total mixture of an oil having a solubilityparameter of 5–12 (cal/cm³)^(1/2).

The invention is also directed to an emulsion hair bleach compositionprepared by combining (i) an aqueous oxidizing agent composition, (ii) apersulfate composition, and (iii) a bleach oil composition containing atleast one hydrophobic oil having a Hildebrand solubility parameterranging from about 5 to 12; in amounts sufficient to provide a mixturecapable of lightening the hair in ten to thirty minutes.

The invention is also directed to a kit for use in bleaching haircomprising three separate components, wherein the first component is anaqueous oxidizing agent composition, the second component is apersulfate composition, and the third composition is a bleach oilcomposition containing at least one hydrophobic oil having a Hildebrandsolubility parameter ranging from about 5 to 12; wherein when said threecomponents are mixed they provide a composition that is operable tolighten hair in ten to thirty minutes.

DETAILED DESCRIPTION

I. The Mixture

The hair bleach composition of the invention is prepared by combining anaqueous oxidizing agent composition, a persulfate composition, and,optionally, a bleach oil composition, mixing well, and applying to thehair. The phrase “total mixture” when referred to “by weight of thetotal mixture” means the mixture obtained by combining the aqueousoxidizing agent composition, the persulfate composition, and,optionally, the bleach oil composition.

A. Active Oxygen

The mixture comprises an active oxygen concentration of about 3 to 5%,preferably about 3.2 to 4.8%, preferably about 3.5 to 4.5% by weight ofthe total mixture. The active oxygen present in the mixture is derivedfrom ingredients that, when reacted, are capable of generating active,or nascent oxygen. Such ingredients include the following:

(1) Ingredients Contributing to Active Oxygen Concentration

(i). Peroxide Oxidizing Agents

Various peroxide oxidizing agents include hydrogen peroxide, ureaperoxide, and the like.

(ii) Persulfates

Various alkaline earth metal, alkali metal, or ammonium persulfate suchas sodium, potassium, ammonium persulfates are suitable. Preferably thepersulfate comprises one or more of an alkali metal, alkaline earthmetal, or ammonium persulfate. Examples of alkali metal persulfatesinclude lithium, sodium, potassium, cesium, and the like. Examples ofsuitable alkaline earth metals include magnesium, calcium, and the like.Particularly preferred are sodium, potassium, and ammonium persulfates.The persulfates are generally in particulate form, have particle sizesranging from about 0.1 to 200 microns.

The persulfates are reactive with the hydrogen peroxide or otherperoxide oxidizing agent present and when the persulfate composition andaqueous oxidizing agent composition, and optionally the bleach oilcomposition are combined, nascent, free oxygen is generated. Withoutbeing bound by this explanation, it is believed that the typicalreaction is as follows:K₂S₂O₈+H₂O₂

H₂S+K₂S+[O—]¹⁰Na₂S₂O₈+H₂O₂

H₂S+Na₂S+[O—]¹⁰(NH₄)₂S₂O₈+H₂O₂

H₂S+(NH₄)₂S+[O—]¹⁰

The free oxygen facilitates faster and more effective bleaching of thehair.

(2) Calculation of Active Oxygen

The active oxygen concentration in the mixture is determined by a methodinvolving quantitation of the ferrous ions present after oxidation ofthe ferrous to ferric ions by the active oxygen present in the sample.The calculation of active oxygen is performed separately on each of thecomponents used to prepare the composition, and the total alkalinity ofthe mixture is obtained mathematically by calculating the totalalkalinity of the separate components used to prepare the mixture andconsidering the ratios and amounts of each of the components combined toprepare the mixture.

(i) Reagents Required:

-   -   (a) ferroin indicator (Fisher Scientific—catalog no. P-69)    -   (b) ceric sulfate (Fisher Scientific—catalog no. Sc 66-1, 0.1 N        solution)    -   (c) ferrous ammonium sulfate hexahydrate—(Sigma-Aldrich—catalog        no. 21,546-6) prepared by dissolving in a 1 liter volumetric        flask, 157 grams of ferrous ammonium sulfate hexahydrate,        400 ml. water, and 100 ml. concentrated sulfuric acid. The flask        is diluted to volume with distilled water.    -   (d) concentrated sulfuric acid

(ii) Procedure: 0.2 grams of the mixture to be analyzed is transferredto a 250 ml. erlenmeyer flask containing 50 ml. distilled water. Themixture is shaken well to dissolve, and any lumps present crushed with aspatula. While shaking the flask 10 ml of 0.4N ferrous ammonium sulfatesolution is pipetted into the flask. The flask is allowed to stand for 1minute. Then 2.5 ml concentrated sulfuric acid and 3 drops ferroinindicator solution are added to the flask. The mixture is then titratedwith 0.1N ceric sulfate until the very first permanent green colorationis seen which is a very sharp endpoint. The active oxygen present in thesample is calculated as follows:${\%\mspace{14mu}{Active}\mspace{14mu}{Oxygen}} = \frac{\left( {a - b} \right) \times N \times 0.8}{W}$wherein:

-   -   a=volume of ceric sulfate used to titrate blank in milliliters    -   b=volume of ceric sulfate used to titrate sample in milliliters    -   N=normality of ceric sulfate    -   W=weight of sample in grams

The mixture of the oxidizing agent composition, the bleach compositionand, optionally the bleach oil composition should provide a mixture thatcontains 3–5% by weight of the total mixture of active oxygen ascalculated according to the above method.

B. Total Alkalinity

The mixture comprises a total alkalinity concentration of about 0.7 to1.2, preferably about 0.85 to 1.15, more preferably about 0.9 to 1.1meq/gm. Total alkalinity is obtained by use of various alkalizing agentsin the mixture. The term “alkalizing agent” means an ingredient having apH of greater than 7, preferably about 7.5 to 11.5, more preferablyabout 8 to 10.5. Total alkalinity refers to the total concentration ofalkalizing agents present, and includes alkalizing agents that are freeto neutralize or react with other components in the composition, andbound alkalizing agents that are already reacted with other ingredientsin the composition yet still contribute to the total alkalinity of thecomposition. For example, the preferred mixtures according to theinvention contain a fatty acid of some type, generally oleic acid. Thealkalizing agent such as monoethanolamine or ammonium hydroxide willreact with the oleic acid to form soap (MEA-oleate or ammonium oleate).The portion of monoethanolamine that has reacted with oleic acid to formsoap is no longer free to react with other ingredients in thecomposition and thereby does not contribute to “free alkalinity” of themixture. A typical example of this reaction is as follows:CH₃(CH₂)₇CH═CH(CH₂)₇COOH+NH₄OH+NH₂CH₂CH₂OH

CH₃(CH₂)₇CH═CH(CH₂)₇COONHCH₂CH₂OH+NH₄ ⁺ ^(−OH)

In the example above, the oleic acid has preferentially reacted withmonoethanolamine to form MEA-oleate, a soap, and is thus bound. The freehydroxyl groups disassociated from the NH₄OH provide free alkalinity tothe composition.

Generally, in order to obtain a total alkalinity concentration withinthe desired range, the concentration of alkalizing agents in the mixturewill range from about 0.1–60%, preferably about 0.5–45%, more preferablyabout 1–35% by weight of the total mixture.

(1) Ingredients Contributing to Total Alkalinity

(i) Ionizable Hydroxyl Compounds

One type of alkalizing agent includes ionizable hydroxyl-containingcompounds such as ammonium hydroxide, or alkali metal or alkaline earthmetal hydroxides such as calcium, sodium, lithium, and the like. In thepreferred mixtures according to the invention the alkalizing agent is acompound containing ionizable hydroxyl groups, preferably ammoniumhydroxide. The ammonium hydroxide dissociates in the composition andcontributes to both the free alkalinity and total alkalinity of themixture. The free alkaline materials penetrate the hair shaft morereadily and promote faster bleaching of the hair. The bound alkalinematerials also contribute to the alkalinity of the composition.

(ii) Amines

Further suitable alkalizing agents include various primary, secondary,and tertiary amines such as monoethanolamine, diethanolamine,triethanolemine, and the like. If fatty acids are present in themixture, the amines may preferentially react with them to form soap,thus binding the amines so that they do not contribute to the freealkalinity of the composition. This, in turn, permits the ionizablehydroxyl containing compounds to provide free alkalinity to thecomposition. Ionizable hydroxyl-containing compounds are better able topenetrate the hair shaft and promote more rapid bleaching of the hair.

(iii) Inorganic Salts

Also suitable as alkalizing agents include inorganic salts such asaluminum, sodium, potassium, and magnesium salts of inorganic or organicacids. Examples of suitable salts include alkali metal and alkalineearth metal silicates, sodium metasilicate, sodium chloride, sodiumsilicate, aluminum citrate, calcium saccharin, calcium salicylate,calcium citrate, calcium benzoate, magnesium acetate, magnesiumascorbate, magnesium PCA, magnesium gluconate, potassium acetate,potassium benzoate, potassium citrate, potassium sorbate, sodiumacetate, sodium ascorbate, sodium silicate, sodium citrate, sodiumgluconate, sodium pyruvate, and mixtures thereof. Particularly preferredinorganic sales are sodium silicate, sodium metasilicate, or mixturesthereof.

The alkalizing agents present in the composition provide a totalalkalinity having the ranges specified.

(2) Calculation of Total Alkalinity

The total alkalinity of the composition comprising a mixture of theoxidizing agent composition, the persulfate composition and, if present,the bleach oil composition is determined by autotritration. Eachseparate component used to prepare the final mixture is assayedseparately for total alkalinity concentration and the total alkalinityvalue of the mixture is calculated mathematically from the amounts andvalues of total alkalinity in the components used to prepare the finalmixture.

(i) Reagents and Equipment:

-   -   (a) Metrohm 716 DMS Titrino Autotitration System or equivalent    -   (b) 150 ml. beaker    -   (c) 0.1 N HCl

(ii) Method:

The Metrohm 7165 DMS Titrino Autotitration System is set to “acid/basetitration with pH electrode” channel. The fixed endpoint is set at pH8.5, for free alkalinity. The final endpoint provides the totalalkalinity value of the sample. The final endpoint is determined by thelarge point of inflection that is seen upon reaching the endpoint,usually a pH ranging from about 4 to 6.

The following equations and factors are programmed into the autitrator:Alkalinity (free or total) in terms of ml. of 0.1N HCl per gram ofsample. ${Alkalinity} = \frac{V \times N}{W \times 0.1}$wherein:

-   -   V=volume of 0.1N HCl used in ml.    -   N=normality of 0.1N HCl, and    -   W=sample weight in grams.

The sample, 0.5 grams, is weighed into a 150 ml beaker. Distilled water,100 ml., is added and mixed well.

The titrator is started, and the amount of 0.1 N HCl required to attainpH 8.5 is noted. The titration is continued by addition of furtheraliquots of 0.1 N HCl in small doses until a large inflection, ordecrease in pH was seen, indicating the final endpoint. The values forfree alkalinity and total alkalinity are multiplied by 0.1 to obtain theresults in meq/gm.

The total alkalinity of the mixture ranges from about 0.7 to 1.2 meq/gm.

C. Hydrophobic Oil

The mixture comprises about 0.5–20% by weight of the total mixture of atleast one hydrophobic oil having a Hildebrand solubility parameter (δ)measured in (cal/cm³)^(1/2) (the square root of calories per cubiccentimeter), ranging from about 5 to 12. Suitable hydrophobic oils arefurther described below. The term “hydrophobic” means that the oil islipophilic in character. The hydrophobic oil is preferably a liquid atroom temperature (25° C.) and has a Hildebrand solubility parameter (δ)value ranging from about 5 to 12, preferably about 6 to 10, morepreferably about 7 to 9. The term “solubility parameter” when used inaccordance with this invention means the Hildebrand solubility parameter(δ) which is calculated according to the formula:δ=(ΔEv/V)^(1/2)wherein ΔEv=heat of vaporization of the particular ingredient, andV=molecular weight/density of the ingredient.

The Hildebrand solubility parameters (δ) are generally available byreferring to standard chemistry textbooks or similar reference manuals.The Journal of the Society of Cosmetic Chemistry, Volume 36, pages319–333, and Cosmetics and Toiletries, Vol. 103, October 1988, pages47–69, both of which are hereby incorporated by reference in theirentirety, list the Hildebrand solubility parameter (δ) values for a widevariety of cosmetic ingredients and how the solubility parameter iscalculated. Suitable hydrophobic oils which have a Hildebrand solubilityparameter (δ) ranging from about 5 to 12 include coconut oil, mineraloil, isopropyl myristate, linseed oil, octyl palmitate, and so on, andthose listed in the above mentioned Journal articles. Oils which havesolubility parameters which are significantly less than 5 are extremelyhydrophobic, and while such oils may promote preferential absorption ofthe active ingredients into the hair shaft by causing the water solubleactives to “repel” the oil and be preferentially pushed into the hairshaft, they are difficult to disperse in the aqueous oxidizing agentcomposition because of their extreme lipophilic character. Oils whichhave Hildebrand solubility parameters which are significantly greaterthan 12 are too hydrophilic and will more readily form part of the waterphase of the aqueous oxidizing agent composition. Accordingly, such oilswill not induce preferential absorption of the water soluble activeingredients into the hair shaft as such active ingredients arecompatible with the hydrophilic ingredients present in the composition.

The mixture applied to the hair may be obtained by combining two,preferably three separate components, mixing well, and immediatelyapplying to the hair. The mixture is capable of bleaching the hair in upto one half the time required for traditional bleach products.Generally, traditional bleaches require about 20 to 60 minutes tolighten hair. The claimed mixture is capable of providing the samedegree of lightening to the hair in 10 to 45 minutes, preferably 10 to30 minutes.

II. The Hair Bleach Components

The preferred hair bleach composition is prepared by combining two,optionally three components, which will be further described herein. Thefirst component is an aqueous oxidizing agent composition. The secondcomponent is a persulfate composition. The third, optional, component isa bleach oil composition. The individual components will contain theingredients required to provide a mixture having the active oxygenconcentration, total alkalinity, and hydrophobic oil concentrations thatare necessary to achieve optimal bleaching of the hair.

A. The Persulfate Composition

The persulfate composition generally comprises a mixture of persulfatecompounds which are capable of bleaching the hair, particulate fillers,and, if desired, inorganic particulate colorants. The persulfatecomposition may be found in the powdered particulate form, or in theform of a cream or paste as described in U.S. Pat. No. 5,888,484; andU.S. patent application Ser. No. 09/774,890, filed Feb. 1, 2001,assigned to Revlon Consumer Products Corporation, naming TeresitaImperial as inventor, both of which are hereby incorporated by referencein their entirety.

1. Persulfates

The persulfate composition comprises about 15–65%, preferably about20–60%, more preferably about 25–55% by weight of the total persulfatecomposition of one or more inorganic persulfates which may be alkalimetal or alkaline earth metal persulfates, or ammonium persulfate.

2. Alkalizing Agents

The persulfate composition preferably contains one or more alkalizingagents. Preferred alkalizing agents are one or more inorganic salts asset forth herein. Suggested ranges of inorganic salts are from about0.1–40%, preferably about 0.5–35%, preferably about 1–30% by weight ofthe total composition.

3. Particulate Fillers

The persulfate composition also preferably comprises one or moreparticulate fillers. Preferably, the persulfate composition comprisesabout 5–60%, preferably about 8–55%, more preferably about 10–50% byweight of the total persulfate composition of the particulate fillers.The term “particulate filler” means a generally inert particulate havinga particle size of about 0.1–250 microns. The particulate fillersprovide volume and, when mixed with the persulfates, dilute thepersulfate particles. A variety of particulate fillers are suitableincluding inorganics, inorganic salts, hydrophilic colloids,carbohydrates, soaps, alkyl sulfates, and the like.

(a) Inorganics

Examples of inorganics include silica, hydrated silica, alumina,attapulgite, bentonite, calcium oxide, chalk, diamond powder,diatomaceous earth, fuller's earth, hectorite, kaolin, mica, magnesiumoxide, magnesium peroxide, montmorillonite, pumice, talc, tin oxide,zeolite, zinc oxide, and the like.

(b) Hydrophilic Colloids

Examples of suitable hydrophilic colloids include hydroxyethylcellulose,locust bean gum, maltodextrin, methylcellulose, agar, dextran, dextransulfate, gelatin, pectin, potassium alginate, sodiumcarboxymethylchitin, xanthan gum, and the like.

(c) Carbohydrates

Examples of suitable carbohydrates include sugars such as glucose,sucrose, maltose, xylose, trehelose, and derivatives thereof, inparticular sugar esters of long chain, C₁₄₋₃₀ fatty acids, as well asdextrins, cellulosics, and derivatives thereof.

(d) Soaps and Alkyl Sulfates

Examples of soaps and alkyl sulfate particles that may act asparticulate fillers include the aluminum, sodium, and potassium salts offatty acids such as aluminum distearate, aluminum isostearate, aluminummyristate, calcium behenate, calcium stearate, calcium behenate,magnesium stearate, magnesium tallowate, potassium palmitate, potassiumstearate, potassium oleate, sodium stearate, sodium oleate, sodiummyristate, sodium palmitate, and the like. Suitable alkyl sulfatesinclude sodium lauryl sulfate, sodium cetyl sulfate, sodium myristylsulfate, sodium octyl sulfate, and the like.

4. Inorganic Colorants

If desired, the persulfate composition may comprise about 0.01–2%,preferably about 0.05–1%, more preferably about 0.1–1% by weight of thetotal persulfate composition of an inorganic colorant. The inorganiccolorant is preferably in the particulate form and will provide a subtlecoloration to the powder composition to make it more aestheticallypleasing for commercial purposes. Particularly preferred for use in thebleach composition is ultramarine blue.

5. Hydrophobic Oil

It may be desirable to include the hydrophobic oil in the persulfatecomposition. If so, the hydrophobic oil must be present in an amountsufficient to provide a mixture having a concentration ranging fromabout 0.5 to 20% by weight of the total mixture of the hydrophobic oil.The suitable hydrophobic oils are those discussed above with respect tothe mixture. If present in the persulfate composition, suggested rangesof hydrophobic oil are from about 0.1–70%, preferably about 0.5–60%,more preferably about 1–50% by weight of the total composition.

6. Other Lipophilic Ingredients

It may be desirable to include one or more oils, or lipophilicingredients, other than the hydrophobic oil in the persulfatecomposition. Suitable oils are lipophilic ingredients that may beliquids, solids, or semi-solids at room temperature (25° C.) which haveHildebrand solubility parameters which are less than 5 or greater than12. Examples of such lipophilic materials include short chainhydrocarbons, polar hydrophilic oils, fatty acids, fatty alcohols,silicone waxes, and so on. If present the other lipophilic ingredientsmay be found in the composition ranging from about 0.1–50%, preferablyabout 0.5–40%, preferably about 1–35% by weight of the totalcomposition.

B. The Aqueous Oxidizing Agent Composition.

The aqueous oxidizing agent composition may be in the solution oremulsion form. If the latter, the emulsion may be in the water-in-oil oroil-in-water form. Further, the emulsion may also be in themicroemulsion form, if desired.

When the aqueous oxidizing agent is in the solution form the compositionpreferably comprises about 1–30% by weight of the total composition ofan oxidizing agent, preferably hydrogen peroxide, and about 70–99% byweight of the total composition of water. Other water solubleingredients may be included in the solution, such as humectants,preservatives, water soluble thickeners, antioxidants, and so on.

When the aqueous oxidizing agent composition is in the emulsion form,the composition preferably comprises about 1–30% of oxidizing agent,preferably hydrogen peroxide, about 50–99% water, and about and0.01–30%, preferably about 0.05–20%, more preferably about 0.1–15% of anoily phase. The aqueous oxidizing agent composition may be in the formof a water-in-oil or oil-in-water emulsion or in the form of atransparent microemulsion wherein the dispersed particles in thecontinuous phase are so small (generally about 5–1500 Å) that thecomposition is optically clear. Examples of suitable microemulsioncompositions are set froth in U.S. Pat. No. 6,315,989, which is herebyincorporated by reference in its entirety. It is also suitable that theaqueous oxidizing agent composition be in the form of a compositioncontaining liquid crystals as set forth in U.S. Pat. No. 6,238,653,which is hereby incorporated by reference in its entirety.

The various ingredients that may be found in the aqueous oxidizing agentcomposition (also referred to as “developer”) are as follows.

1. Oxidizing Agent.

Preferably the oxidizing agent is hydrogen peroxide, although othersuitable peroxides such as urea peroxide, sodium perborate, etc. may beused as well. Preferably the aqueous oxidizing agent compositioncontains hydrogen peroxide. The oxidizing agent contributes to formationof active oxygen when the various components are combined.

2. Hydrophobic Oil

The hydrophobic oil may be present in the aqueous oxidizing agentcomposition if this composition is in the emulsion form. If so,suggested ranges are about 1–85%, preferably about 3–70%, preferablyabout 5–65% by weight of the total composition. The hydrophobic oilsthat are suitable are as set forth herein.

3. Other Oils

If the aqueous oxidizing agent is in the form of an emulsion, thecomposition may comprise one or more oily or lipophilic ingredientseither alone or in combination with the hydrophobic oil. Suitablelipophilic ingredients may be liquids, semi-solids, or solids oils atroom temperature (25° C.) which have Hildebrand solubility parameters(δ) which are less than 5 or greater than 12. Examples of suchlipophilic materials include short chain hydrocarbons, polar hydrophilicoils, fatty acids, fatty alcohols, silicone waxes, and so on. If suchother lipophilic ingredients are present, suggested ranges are about0.1–50%, preferably about 0.5–35%, more preferably about 1–30% by weightof the total composition.

4. Humectants

Humectants may be present in the aqueous oxidizing agent composition. Ifso, suggested ranges are from about 0.01–10%, more preferably about0.05–8%, most preferably about 0.1–5% by weight of the total compositionof humectant. Suitable humectants include monomeric, homopolymeric,and/or block copolymeric ethers as well as mono-, di-, or polyhydricalcohols.

Suitable ethers are formed by the polymerization of monomeric alkyleneoxides, generally ethylene or propylene oxide. Such polymeric ethershave the following general formula:

wherein R is H or lower alkyl and n is the number of repeating monomerunits, and ranges from 1 to 500.

Also suitable are polyols such as glycerine or C₁₋₄ alkylene glycols andthe like. Particularly preferred are C₁₋₄ alkylene glycols, inparticular propylene and/or butylene glycol and ethoxydiglycol.

Suitable mono-, di-, or polyhydric alcohols include glycerin, butyleneglycol, ethylene glycol, propylene glycol, and so on.

5. Water Soluble Thickeners

The aqueous oxidizing agent composition may contain one or more watersoluble thickeners. If present suggested ranges are from about 0.1–25%,preferably about 0.5–20%, more preferably 1–15% by weight of the totalcomposition. Suitable thickeners include

(a) Acrylic Copolymer Thickeners

Suitable acrylic copolymeric thickeners are comprised of monomers A andB wherein A is selected from the group consisting of acrylic acid,methacrylic acid, and mixtures thereof; and B is selected from the groupconsisting of a C₁₋₂₂ alkyl acrylate, a C₁₋₂₂ alky methacrylate, andmixtures thereof. Preferably, the A monomer comprises one or more ofacrylic acid or methacrylic acid, and the B monomer comprises isselected from the group consisting of a C₁₋₁₀, most preferably C₁₋₄alkyl acrylate, a C₁₋₁₀, most preferably C₁₋₄ alkyl methacrylate, andmixtures thereof. Most preferably the B monomer is one or more of methylor ethyl acrylate or methacrylate. Most preferably, the acryliccopolymer is supplied in an aqueous solution having a solids contentranging from about 10–60%, preferably 20–50%, more preferably 25–45% byweight of the polymer, with the remainder water. Preferably, thethickening agent is a polymer comprised of A, B, and C monomers whereinA and B are as defined above, and C has the general formula:

Preferably, in the copolymer used for the secondary thickening agent inthe preferred embodiment of the invention, A and B are as above defined;and in the C monomer Z is (CH₂)_(m), m is 1–2, n is 2, and o is 2–100,and R is a C₁₂₋₂₂ straight or branched chain alkyl. More preferably inthe C monomer m is 1, n is 2, o is 10, and R is C₁₈ or stearyl, and thecompound is steareth-10 allyl ether/acrylate copolymer, which may bepurchased from Allied Colloids under the tradename Salcare SC90.

Also suitable is an aqueous solution of an acrylic polymer comprised ofmonomers A and B wherein A is selected from the group consisting ofacrylic acid, methacrylic acid, and mixtures thereof; and B is selectedfrom the group consisting of a C₁₋₂₂ alkyl acrylate, a C₁₋₂₂ alkymethacrylate, and mixtures thereof. Preferably, the A monomer comprisesone or more of acrylic acid or methacrylic acid, and the B monomercomprises is selected from the group consisting of a C₁₋₁₀, mostpreferably C₁₋₄ alkyl acrylate, a C₁₋₁₀, most preferably C₁₋₄ alkylmethacrylate, and mixtures thereof. Most preferably the B monomer is oneor more of methyl or ethyl acrylate or methacrylate. Most preferably,the acrylic copolymer is supplied in an aqueous solution having a solidscontent ranging from about 10–60%, preferably 20–50%, more preferably25–45% by weight of the polymer, with the remainder water. Thecomposition of the acrylic copolymer may contain from about 0.1–99 partsof the A monomer, and about 0.1–99 parts of the B monomer. Preferably,the acrylic copolymer contains enough of the A monomer to enableionization in a basic solution, thereby causing the ionized carboxylicacid groups in the polymer to repel each other, and thereby “swallow”water. Particularly preferred acrylic copolymer solutions suitable foruse in the developer composition include those sold by Seppic, Inc.,under the tradename Capigel, in particular, Capigel 98, which is a whiteliquid having a pH of 2 to 4, a solids content of about 29–31, a densityof 1.04 to 1.08, and a viscosity of 700–1000 millipascal seconds at 25°C.

(b) Associative Thickeners

Various other types of associative thickeners may be present, includingwater soluble urethane homo- and copolymers, and the like.

6. Nonionic Surfactants

If desired, the aqueous developer composition may contain one or morenonionic surfactants. Recommended ranges are 0.01–10%, preferably0.05–8%, more preferably 0.1–7% by weight of the total composition.

(a) Alkoxylated Alcohols

Suitable nonionic surfactants include alkoxylated alcohols, or ethers,formed by the reaction of an alcohol with an alkylene oxide, usuallyethylene or propylene oxide. Preferably the alcohol is a fatty alcoholhaving 6 to 30 carbon atoms, and a straight or branched, saturated orunsaturated carbon chain. Examples of such ingredients include Beheneth5-30, which is formed by the reaction of behenyl alcohol and ethyleneoxide where the number of repeated ethylene oxide units is 5 to 30;Ceteareth 2-100, formed by the reaction of a mixture of cetyl andstearyl alcohol with ethylene oxide, where the number of repeatingethylene oxide units in the molecule is 2 to 100; Ceteth 1-45 which isformed by the reaction of cetyl alcohol and ethylene oxide, and thenumber of repeating ethylene oxide units is 1 to 45, and so on.Particularly preferred is Ceteareth 20, which is the reaction product ofa mixture of cetyl and stearyl alcohol with ethylene oxide, and thenumber of repeating ethylene oxide units in the molecule is 20.

(b) Alkoxylated Carboxylic Acids

Also suitable as the nonionic surfactant are alkyoxylated carboxylicacids, which are formed by the reaction of a carboxylic acid with analkylene oxide or with a polymeric ether. The resulting products havethe general formula:

where RCO is the carboxylic ester radical, X is hydrogen or lower alkyl,and n is the number of polymerized alkoxy groups. In the case of thediesters, the two RCO— groups do not need to be identical. Preferably, Ris a C₆₋₃₀ straight or branched chain, saturated or unsaturated alkyl,and n is from 1–100.

(c) Sorbitan Derivatives

Other suitable nonionic surfactants include alkoxylated sorbitan andalkoxylated sorbitan derivatives. For example, alkoxylation, inparticular, ethoxylation, of sorbitan provides polyalkoxylated sorbitanderivatives. Esterification of polyalkoxylated sorbitan providessorbitan esters such as the polysorbates. Examples of such ingredientsinclude Polysorbates 20–85, sorbitan oleate, sorbitan palmitate,sorbitan sesquiisostearate, sorbitan stearate, and so on.

The aqueous oxidizing agent composition may also comprise a variety ofother ingredients including cationic, amphoteric, or zwitterionicsurfactants, preservatives.

C. The Bleach Oil Composition

The third component that may be used to prepare the mixture applied tohair, is a bleach oil composition. The term “bleach oil composition”means a liquid composition that is mixed with the aqueous oxidizingagent composition and the persulfate composition to provide a mixturesuitable for bleaching hair. Generally the bleach oil composition willcontain one or more ingredients that are capable of conditioning hairand ameliorating the drying effects that bleaches sometimes have onhair. In the preferred embodiment of the invention the mixture that isapplied to hair is obtained by combining an aqueous oxidizing agentcomposition, a persulfate composition, and a bleach oil composition. Inthe preferred embodiment, the hydrophobic oil is preferably present aspart of the bleach oil composition rather than in the aqueous oxidizingagent composition.

The bleach oil composition is preferably in the emulsion form, and maybe a water-in-oil or oil-in-water emulsion or microemulsion. The bleachoil composition generally comprises about 1–75%, preferably about 2–70%,more preferably about 5–65% by weight of the total composition of water,and about 0.1–50%, preferably about 0.5–45%, more preferably about 1–40%by weight of the total composition of hydrophobic oil. The hydrophobicoils are as mentioned above with respect to the aqueous oxidizing agentcomposition. In addition, the bleach oil composition may comprise otheringredients such as surfactants, alkalizing agents, antioxidants,humectants, other lipophilic ingredients, all in the amounts taughtabove with respect to the aqueous oxidizing agent composition.Additionally, the bleach oil may be found in the microemulsion formwherein the dispersed particles in the emulsion exhibit a small particlesize, e.g. from about 5 to 1500 Å.

The preferred bleach oil composition contains at least one alkalizingagent that is capable of contributing to the total alkalinity of themixture. Suggested ranges of alkalizing agent found in the bleach oilare about 0.1–50%, preferably about 0.5–45%, more preferably about 1–40%by weight of the total composition. Preferred is where the bleach oilcontains an ionizable hydroxyl containing compound as the alkalizingagent.

III. The Method

The oxidizing agent composition and the persulfate composition and,optionally, the bleach oil composition are combined in sufficient ratiosto yield a final mixture that comprises an active oxygen concentrationof about 3 to 5% by weight of the total composition, a total alkalinityconcentration of about 0.7–1.2 meq/gm., and 0.5–20% by weight of thetotal mixture of an oil having a Hildebrand solubility parameter of5–12. Generally, determination of suitable ratios of each of the two orthree components is well within the skilled artisan's capabilities.Generally, in the preferred embodiment of the invention, the mixturecomprises about 20–80% by weight of the total mixture of the aqueousoxidizing agent composition, about 5–40% by weight of the total mixtureof persulfate composition, and, optionally, about 5–30% by weight of thetotal mixture of the bleach oil composition.

The invention will be further described in connection with the followingexamples, that are set forth for the purposes of illustration only.

EXAMPLE 1

An aqueous oxidizing agent composition (or developer) was made accordingto the following formula:

w/w % Water 68.91 EDTA 0.02 Laureth 23 1.50 Cetearyl alcohol 1.35 Sodiumlauryl sulfate 0.075 Sodium cetearyl sulfate 0.075 Cetearyl alcohol 1.00Hydrogen peroxide (35% aqueous solution) 26.00 Phosphoric acid 0.02Disodium phosphate 0.05 Steareth-10 allyl ether/acrylates copolymer 1.00

A powdered persulfate composition was made according to the followingformula:

w/w % Potassium persulfate 40.00 Sodium persulfate 10.00 Ammoniumpersulfate 15.00 Sodium silicate 20.00 Hydrated silica 1.00 Sodiumlauryl sulfate 2.75 Tetrasodium EDTA 1.25 Sodium metasilicate 7.00Hydroxyethylcellulose 2.00 Xanthan gum 1.00

A bleach oil composition made according to the following formula:

w/w % Water 20.60 Tetrasodium EDTA 0.80 Isopropanol amine 10.00Ethoxydiglycol 8.00 Laureth 4 15.00 Oleic acid 13.00 Ethanolamine 3.00Isopropyl myristate 9.50 Coconut oil 5.00 Ammonium hydroxide 13.00Fragrance 1.00 Hydrolyzed marine collagen 0.50 Wheat amino acids 0.50Sodium benzotriazolyl sulfonate/buteth 3/ 0.10 Tributyl citrate

The mixture to be applied to hair was prepared by combining 28.5 gramsbleach oil, 123.5 grams of the aqueous oxidizing agent composition, and47.5 grams of the persulfate composition and mixing well. Thecomposition had an active oxygen concentration of 3.52% by weight of thetotal mixture, a total alkalinity concentration of 0.955 meq/gm, and theamount of hydrophobic oil in the mixture was 2% by weight of the totalmixture.

The mixture was used to dye light brown virgin hair swatches weighingabout 1.5 grams per swatch. The mixture was applied to the swatches, andthe color measured at 10 minutes and 30 minutes using the datacolorcolor tools QC (version 1.2.1) spectrocolorimeter. The chromaticity (c*)of the swatches was measured from values of a*, b*, in the L*, a*, andb* international color notation system. The degree of lightening wasdetermined from the change in L (lightening), a (red), and b (yellow)values. The results were as follows:

Time (minutes) L a b 10 45.50 9.40 23.49 30 57.77 9.40 29.04

EXAMPLE 2

Comparative bleach oil compositions were prepared as follows:

Sample 1 2 3 4 5 6 7 8 9 Water 20.6 35.1 20.6 20.6 20.6 20.6 20.6 20.620.6 Tetrasodium EDTA 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8Isopropanolamine 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0Ethoxydiglycol 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 Laureth-4 15.0 15.015.0 15.0 24.5 24.5 15.0 15.0 15.0 Oleic acid 13.0 13.0 13.0 13.0 13.013.0 13.0 13.0 13.0 Ethanolamine 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0Isopropyl myristate 9.5 — — 14.5 — — — — — Coconut oil 5.0 — — — 5.0 — —— — Mineral Oil — — — — — 5.0 — — — Oleyl alcohol — — — — — — — 14.5 —Triacetin — — — — — — — — 14.50 Benzyl alcohol — — — — — — 14.5 — —Propylene glycol — — 14.5 — — — — — — Ammonium hydroxide 13.0 13.0 13.013.0 13.0 13.0 13.0 13.0 13.0 Fragrance 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.01.0 Hydrolyzed collagen* 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Wheat aminoacids 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 UV absorber** 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 0.1 *hydrolyzed marine collagen **sodium benzotriazolylsulfonate/buteth-3/tributyl citrate

The above compositions were combined with the powdered persulfatecomposition and aqueous oxidizing agent composition set forth in Example1 in the following ratios: 28.5 grams bleach oil, 123.5 grams aqueousoxidizing agent composition, and 47.5 powdered persulfate composition.Light brown virgin hair swatches (1.5 grams per swatch), were coloredusing the compositions and the chromaticity of the swatches was measuredat 10 and 30 minutes in accordance with the equipment and methodsmentioned in Example 1.

Sample L L ΔL ΔL ΔE ΔE a a b b (10′) (30′) (10′) (30′) (10′) (30′) (10′)(30′) (10′) (30′) 1 45.50 57.77 9.40 9.40 23.49 29.04 2 43.75 54.45−1.74 −3.32 1.98 3.67 9.66 9.74 22.57 27.50 3 44.07 52.98 −1.42 −4.791.58 4.98 9.57 10.06 22.81 27.84 4 44.38 58.42 −1.11 0.66 2.04 1.51 9.248.62 21.79 27.93 5 44.66 57.63 −0.83 −0.14 2.13 0.81 9.12 8.99 21.5428.36 6 46.39 57.38 0.89 −0.38 1.03 1.62 9.34 9.01 22.98 27.51 7 44.0854.97 −1.42 −2.80 1.52 3.04 9.50 9.51 22.93 27.87 8 44.54 56.08 −0.96−1.69 1.15 1.72 9.44 9.72 22.86 28.89 9 44.07 55.49 −1.43 −2.27 1.812.37 9.16 9.43 22.41 28.39wherein ΔL=the difference in lightening between sample 1 and comparativesamples 2–9 in 10 and 30 minutes, L (10′) and L(30′); and ΔE=thedifference in overall color change between sample 1 and comparativesamples 2–9 in 10 and 30 minutes. The ΔE was calculated as follows:ΔE=(L−L _(o))²+(a−a _(o))²+(b−b _(o))²wherein L is the is the level of darkness or lightness, a is the red andgreen components, and b is yellow and blue components, and wherein thesubscript o means prior to dyeing.

The solubility parameter δ in (cal/cm³)^(1/2) for the oils used insamples 1–9 are referenced below:

Oil δ Mineral oil 7.09 Isopropyl myristate 8.02 Oleyl alcohol 8.95Triacetin 10.77 Benzyl alcohol 12.31 Propylene glycol 14.00 Water 23.40Coconut oil 8.1

Samples 2, 3, and 7 do not contain a hydrophobic oil having a δ rangingfrom about 5 to 12 (cal/cm³)^(1/2). Accordingly, it is seen that whenthe hydrophobic oil is not present the hair swatches exhibit inferiorlightening when compared to the compositions where a hydrophobic oilhaving a δ ranging from about 5 to 12 is present.

EXAMPLE 3

The mixture of the aqueous oxidizing agent composition, the persulfatecomposition, and the bleach oil composition set forth Example 1 wascompared with mixtures obtained by combining the aqueous oxidizing agentcomposition and persulfate composition of Example 1 with the bleach oilcomposition found in various competitive products. The total alkalinity,active oxygen, and hydrophobic oil concentration of the mixtures wascalculated.

MIXTURE Bleach Oil 1 2 3 4 5 6 7 8 Total 2.143 1.237 2.72 0.95 1.34 0.860.647 2.043 alkalinity (meq/g) Free 1.277 0.375 2.360 0.500 0.820 0.3200.196 1.135 alkalinity meq/gml Aqueous 1 1 1 1 1 1 1 1 oxidizing agentActive 4.23 4.23 4.23 4.23 4.23 4.23 4.23 4.23 oxygen (%) Persulfate 1 11 1 1 1 1 1 Total 2.724 2.724 2.724 2.724 2.724 2.724 2.724 2.724alkalinity (meq/gm) Free 2.191 2.191 2.191 2.191 2.191 2.191 2.191 2.191alkalinity (meq/gm) Mixture 1 + 2 + 3 + 4 + 5 + 6 + 7 + 8 + of: 1 + 11 + 1 1 + 1 1 + 1 1 + 1 1 + 1 1 + 1 1 + 1 Total 0.955 0.825 1.037 0.7840.840 0.771 0.741 0.940 Alkalinity (meq/gm) Free 0.704 0.575 0.859 0.5930.639 0.567 0.550 0.684 Alkalinity (meq/gm) Active 3.52 3.52 3.52 3.523.52 3.52 3.52 3.52 Oxygen (% by weight of mixture) *Mixture: 1. 123.5grams aqueous oxidizing agent composition of Example 1 + 47.5 grams ofpersulfate composition of Example 1 + 28.5 grams of bleach oilcomposition of Example 1. 2. 123.5 grams aqueous oxidizing agentcomposition of Example 1 + 47.5 grams of persulfate composition ofExample 1 + 28.5 grams of Clairol Maxi Blonde Bleach oil, the ingredientlabeling on the product identifying the composition as containing: oleicacid, SD alcohol 40, water, PEG-5 soyamine, ethyl hydroxymethyl oleyloxazoline, nonyl nonoxynol 49, trideceth-6, ethoxydiglycol, ammoniumhydroxide, fragrance, EDTA, D&C Violet No. 2, D&C Green No. 6. 3. 123.5grams aqueous oxidizing agent composition of Example 1 + 47.5 grams ofpersulfate composition of Example 1 + 28.5 grams Herbal Essences BleachBlonding oil, the ingredient labeling on the product identifying thecomposition as containing: water, ethanolamine, propyleneglycol,soytrimonium chloride, C12–15 pareth-3, oleic acid, ethoxydiglycol,steareth-21, fragrance, oleamide MIPA, crataegus monogina fruit extract,spiraea ulmaria flower extract,anthemis nobilis flower extract,tocopheryl acetate, magnolia acuminata bark extract, cocamidopropylbetaine, C11–15 pareth-9, hydrolyzed vegetable protein,PEG-150/stearyl/SMDI copolymer, erythrobic acid, EDTA, sodium sulfite,sodium metasilicate, Polysorbate 20. 4. 123.5 grams aqueous oxidizingagent composition of Example 1 + 47.5 grams of persulfate composition ofExample 1 + 28.5 grams Feria 200 Blonding oil, the ingredient labelingon the product identifying the composition as containing: deceth-3,deceth-5, water, oleic acid, propyleneglycol, oleth-30, ammoniumhydroxide, butoxydiglycol, oleyl alcohol, fragrance. 5. 123.5 gramsaqueous oxidizing agent composition of Example 1 + 47.5 grams ofpersulfate composition of Example 1 + 28.5 grams Feria 205 Blonding oil,the ingredient labeling on the product identifying the composition ascontaining: water, cetearyl alcohol, propyleneglycol, deceth-3,laureth-12, ammonium hydroxide, oleth-30, lauric acid, glycoldistearate, polyquaternium-22, ethanolamine, silica dimethyl silylate,pentasodium pentetate, carbomer, fragrance. 6. 123.5 grams aqueousoxidizing agent composition of Example 1 + 47.5 grams of persulfatecomposition of Example 1 + 28.5 grams of Frost and Glow blonding oil,the ingredient labeling on the product identifying the composition ascontaining: MEA-oleate, water, isopropyl myristate, laureth-4, isopropylalcohol, ethoxydiglycol, oleyl alcohol, ethanolamine, simmondsiachinensis (jojoba) seed oil, fragrance, tetrasodium EDTA. 7. 123.5 gramsaqueous oxidizing agent composition of Example 1 + 47.5 grams ofpersulfate composition of Example 1 + 28.5 grams of Garnier NutrisseLightening Kit bleach oil, the ingredient labeling on the productidentifying the composition as containing: deceth-3, deceth-5, water,oleic acid, propyleneglycol, oleth-30, ammonium hydroxide,butoxydiglycol, oleyl alcohol, fragrance. 8. 123.5 grams aqueousoxidizing agent composition of Example 1 + 47.5 grams of persulfatecomposition of Example 1 + 28.5 grams of Clairol XtremeFX IndustrialBlonde bleach oil, the ingredient labeling on the product identifyingthe composition as containing: oleic acid, oleth-2, water,propyleneglycol, ethanolamine, isopropyl alcohol, soytrimonium chloride,ethoxydiglycol, C12–15 pareth-3, hexyleneglycol, ammonium hydroxide,fragrance, erythorbic acid, sodium sulfate, EDTA.

The above mixtures were used to dye light brown virgin hair swatchesweighing about 1.5 grams per swatch. The mixtures were applied to theswatches, and the color measured at 10 minutes and 30 minutes using thedatacolor color tools QC (version 1.2.1) spectrocolorimeter. Thechromaticity (c*) of the swatches was measured from values of a*, b*, inthe L*, a*, and b* international color notation system. The degree oflightening was determined from the change in L (lightening), a (red),and b (yellow) values. The results were as follows: accordance with theequipment and methods mentioned in Example 1.

L L ΔL ΔL ΔE ΔE a a b b Mixture (10′) (30′) (10′) (30′) (10′) (30′)(10′) (30′) (10′) (30′) 1 + 1 + 1 45.5 57.7 9.40 9.40 23.49 29.04 2 +1 + 1 43.68 54.51 −1.81 −3.26 2.78 3.46 9.19 9.38 21.39 27.88 3 + 1 + 143.52 54.62 −0.20 −3.14 2.66 3.34 9.22 9.59 21.73 27.94 4 + 1 + 1 43.2254.51 −2.27 −3.26 2.77 3.46 9.33 9.38 21.91 27.88 5 + 1 + 1 44.84 56.89−0.66 −0.88 1.35 1.06 9.39 9.52 22.31 28.47 6 + 1 + 1 42.26 54.89 −3.23−2.88 4.19 3.18 9.12 9.58 20.85 27.69 7 + 1 + 1 45.56 56.43 0.34 −1.340.90 1.86 9.49 9.19 22.66 27.77 8 + 1 + 1 44.45 54.90 −0.11 −2.87 2.043.41 9.02 9.08 23.57 27.23

The above results illustrate that the claimed mixture, containing ahydrophobic oil and the active oxygen and total alkalinity concentrationwithin the claimed ranges, provides a bleach composition that providesimproved lightening to hair in 30 minutes when compared to the otherproducts.

EXAMPLE 4

An aqueous oxidizing agent composition (or developer) was made accordingto the following formula:

w/w % Water 67.41 EDTA 0.02 Isopropyl alcohol 2.00 Laureth 23 2.00Cetearyl alcohol, Sodium 1.50 Lauryl Sulfate, Sodium cetearylsulfate(90:5:5) Cetearyl alcohol 1.00 Hydrogen peroxide (35% aqueoussolution) 26.00 Phosphoric acid 0.02 Disodium phosphate 0.05

A powdered persulfate composition was made according to the followingformula:

w/w % Potassium persulfate 45.00 Sodium persulfate 10.00 Ammoniumpersulfate 10.00 Sodium silicate 20.00 Hydrated silica 0.80 Sodiumlauryl sulfate 3.45 Tetrasodium EDTA 1.50 Sodium Metasilicate 7.25Hydroxyethylcellulose 2.00

A bleach oil composition made according to the following formula:

w/w % Water 21.70 Tetrasodium EDTA 0.80 Isopropanolamine 10.00Ethoxydiglycol 8.00 Laureth-4 15.00 Oleic acid 12.50 Ethanolamine 3.00Isopropyl myristate 15.00 Ammonium hydroxide 13.00 Fragrance 1.00

The mixture to be applied to hair was prepared by combining 30 gramsbleach oil, 120 grams of the aqueous oxidizing agent composition, and 60grams of the persulfate composition and mixing well.

Half head tests were conducted on models with brown hair. The abovemixture was applied to one half of the models' heads. The mixture wasleft on the hair for 15 minutes, then removed by rinsing well withwater.

Then Feria 200, combined according to package instructions, was appliedto the other, untreated half of the model's head. The ingredientlabeling for the components of the Feria 200 product is reproducedbelow:

Aqueous Oxidizing Agent Composition (developer): water, hydrogenperoxide, cetearyl alcohol, trideceth-2 carboxamide MEA, ceteareth-30,glycerin, pentasodium pentetate, sodium stannate, tetrasodiumpyrophosphate.

Powdered Persulfate Composition: potassium persulfate, sodiumpersulfate, ammonium chloride, sodium metasilicate, sodium silicate,water, EDTA, hydrated silica, sodium lauryl sulfate.

Bleach Oil Composition: deceth-3, deceth-5, water, oleic acid, propyleneglycol, oleth-30, ammonium hydroxide, butoxydiglycol, oleyl alcohol,fragrance.

The Feria 200 mixture was left on the models' heads for 30 minutes, thenremoved by rinsing well with water. The two sides were visually comparedby an experienced hair color technician. It was noted that the sidetreated with the mixture of Example 4 after 15 minutes exhibited thesame degree and nature of lightening as the side treated with Feria 200after 30 minutes. Accordingly, the mixture of claim 4 provided the samedegree of lightening in one half the time.

While the invention has been described in connection with the preferredembodiment, it is not intended to limit the scope of the invention tothe particular form set forth but, on the contrary, it is intended tocover such alternatives, modifications, and equivalents as may beincluded within the spirit and scope of the invention as defined by theappended claims.

1. An emulsion hair bleach composition prepared by combining (i) anaqueous oxidizing agent composition, and (ii) a persulfate compositioncomprising an organic oil having a Hildebrand solubility parameter of5–12 (cal/cm³)^(1/2), and in amounts sufficient to provide a mixturecontaining: (a) an active oxygen concentration of about 3 to 5% byweight of the total mixture, (b) a total alkalinity concentration ofabout 0.7–1.2 meq/gm., and (c) about 0.5–20% by weight of the totalmixture of an oil having a Hildebrand solubility parameter of 5–12(cal/cm³)^(1/2).
 2. The mixture of claim 1 wherein the active oxygen isprovided by one or more of peroxide oxidizing agents or persulfates. 3.The mixture of claim 2 wherein the peroxide oxidizing agent is hydrogenperoxide.
 4. The mixture of claim 2 wherein the persulfate is selectedfrom the group consisting of alkaline earth metal persulfate, alkalimetal persulfate, ammonium persulfate, and mixtures thereof.
 5. Themixture of claim 1 wherein the active oxygen concentration is about 3.2to 4.8% by weight of the total mixture.
 6. The mixture of claim 1wherein the total alkalinity is provided by one or more alkalizingagents.
 7. The mixture of claim 6 wherein the alkalizing agents eitheralone or in combination have a pH ranging from about 7.5 to about 11.5.8. The mixture of claim 7 wherein the alkalizing agent is selected fromthe group consisting of ionizable hydroxyl containing compound, amine,inorganic salt, and mixtures thereof.
 9. The mixture of claim 8 whereinthe ionizable hydroxyl containing compound is selected from the groupconsisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide,and mixtures thereof.
 10. The mixture of claim 8 wherein the amine is aprimary amine.
 11. The mixture of claim 10 wherein the amine is a C₁₋₁₀alkanolamine.
 12. The mixture of claim 11 wherein the alkanolamine ismonoethanolamine.
 13. The mixture of claim 8 wherein the inorganic saltis selected from the group consisting of alkali metal silicate, alkalineearth metal silicate and mixtures thereof.
 14. The mixture of claim 1wherein the total alkalinity includes alkalizing agents that are free toneutralize with other components in the composition and bound alkalizingagents that are already reacted wit other ingredients in thecomposition.
 15. The mixture of claim 1 wherein the organic oil has aHildebrand solubility parameter ranging from about 7 to about 9(cal/cm³)^(1/2).
 16. The mixture of claim 1 wherein the organic oilhaving Hildebrand solubility parameter of 5–12 (cal/cm³)^(1/2) isselected from the group consisting of coconut oil, mineral oil,isopropyl myristate, linseed oil, octyl palmitate, and mixtures thereof.17. The mixture of claim 1 which is prepared by combining an aqueousoxidizing agent composition, a persulfate composition, and a bleach oilcomposition.
 18. The mixture of claim 17 wherein the aqueous oxidizingagent composition is a solution or emulsion of hydrogen peroxide. 19.The mixture of claim 18 wherein the aqueous oxidizing agent compositionis an emulsion.
 20. The mixture of claim 18 wherein the aqueousoxidizing agent composition comprises, by weight of the totalcomposition: about 1–30% hydrogen peroxide, about 50–99% water, andabout 0.1–30% by weight of the total composition of an oily phase. 21.The mixture of claim 20 wherein the oily phase comprises silicone. 22.The mixture of claim 17 wherein the persulfate composition comprises, byweight of the total persulfate composition: about 15–65% of one or moreinorganic persulfates, about 0.1–5% of one or more inorganic salts, andabout 5–60% of one or more particulate fillers.
 23. The composition ofclaim 22 which is in the powdered form.
 24. The composition of claim 22which is in the cream or paste form.
 25. The composition of claim 24further comprising an oil which is a hydrophobic oil, a lipophilicingredient or mixtures thereof.
 26. The mixture of claim 17 wherein thebleach oil composition comprises, by weight of the total bleach oilcomposition: about 1–75% water, about 0.1–50% hydrophobic oil, and about0.1–50% of one or more alkalizing agents.
 27. The composition of claim26 wherein the hydrophobic oil is selected from the group consisting ofcoconut oil, mineral oil, isopropyl myristate, and mixtures thereof. 28.An emulsion hair bleach composition prepared by combining (i) an aqueousoxidizing agent composition, (ii) a persulfate composition containing atleast one organic oil having a Hildebrand solubility parameter rangingfrom about 5 to 12 (cal/cm³)^(1/2), and (iii) a bleach oil compositionin amounts sufficient to provide a mixture capable of lightening thehair in ten to thirty minutes.
 29. A kit for use in bleaching haircomprising three separate components, wherein the first component is anaqueous oxidizing agent composition, the second component is apersulfate composition, and the third composition is a bleach oilcomposition wherein the persulfate composition contains at least onehydrophobic organic oil having a Hildebrand solubility parameter rangingfrom about 5 to 12 (cal/cm³)^(1/2); wherein when said three componentsare mixed they provide a mixture that lightens hair in ten to thirtyminutes.
 30. The kit of claim 1 wherein the aqueous oxidizing agentcomposition comprises about 20–80% by weight of the total mixture, thepersulfate composition comprises about 5–40% by weight of the totalmixture, and the bleach oil composition comprises about 10–30% by weightof the total mixture.